Hydrogenolysis process for the production of a good quality gas oil and gasoline from a heavy residuum hydrocarbon oil



Feb- 3 1953 w. c. LANNING HYDROGENOLYSIS PROCESS FOR THE PRODUCTION OF' A GOOD QUALITY GAS OIL AND GASOLINE FROM A HEAVY RESIDUUM HYDROCARBON OIL Filed Nov. 25, 1943 INVENTOR. w c LANNING A T Tom/EVS Patented Feb. 3, 1953 UNITED STATES PATENT OFFICE Yl-Villianrl C. lfianning,` Bartlesville, kla., assignor to Phillips Petroleum Company,a corporation A of'Delaware Application? November 25, 1949, SerialNo; 129,441 claims. "(01. 19e-14.11)

This invention relates'to animprovedprocess forthe hydrogenolysis of hydrocarbonaceousmaterials. `In one of its morespecific aspects it relates to a process for the hydrogenolysis of petroleum residues such `as topped crude,` reduced crude; cracking residuum, shale oil, and the like. One specific embodimentof the invention relates to a novel'V process forV thehydrogenolysisfof hydrocarbonaceous materials, the resulting products of which include good `quality vgasoline and diesel fuel.

i The hydrogenolysis of residual hydrocarbon stocksiand like -heavy hydrocarbons fto produce lower Lboilinghydrocarbonsis not a newart. V'It Wasfirstdeveloped in Germany, the eld being quitecompletely explored. "Howeventhe process has never enjoyed Wideispreaduse for several reasons. `For example, suchfa'process is considerablyexpensive, particularly in theoutlay necessary for processing equipment 'and for the`production of the large quantities of hydrogen znecessary. Another reason is that depending on the feed, only onew good quality product is obtained, `thatfis, gasoline or 'diesel' fuel. The `reas'onfor this apparently lies `in the `fact that hydrog-enolysis products from parafnic feed provide highv quality diesel fuel with good cetane number and products from `aromatic feed'provide good quality gasolines with high octane numbers. Obviously, it would be toeveryones advantage if a hydrogenolysis `process `were developed whereby b-oth high 'quality-:gasoline-'and diesel fu'eli-Were produced.

Anobject of this invention is to provide animproved process for the hydrogenolysisfof hydrocarbonaceous materials.

1 Another object f is toprovide a''process 'for the hydrogenolysis' of residual fractions *such as" from crude oil.

Anothe'robj ect Vvof this'invention'is tdprovide` a `hydrogenolysis process `for `the treatment' of `hy drocarbons whereby 'both good quality .gasoline and gas `oil ordi'esel fuel are obtained.

`Still another object is to provide a processior the treatment 'of oilsv containing bothf'ar'omatics and pararlins whereby Veach of these groups of materials is advantageously treated to fprov'ide a totali product including improved-gasoline and Agas oil.

l I` lhave found that the treatment ofA ai'mixtu-re of parafns and aromatics providesV products inferior to those produced by separate treatment. This may be caused by the fact that the optimum hydrogenolysis conditions for paraffinsare 'not optimum for aromatics.

I have discovered an improved process for the treatment of a residuum hydrocarbon material containing both paraffins and aromatics whereby such a material is first extracted to separatesame into parainic and aromatic fractionatheseV frac- 2 tions 1 then being individually treated in` ahydrogenolysis` processlat optimum conditions. By following the teachings of my process maximum yields of high-qualityproductsfare obtained.

It isto be understood thattlief-aromaticfra-ctions separated bythe processof this invention mayalso contain some cycloparainswhich-are preferentially dissolved by the i solvent :for -the aromatics. The presence `of these"materials has not `been found to `cause anyfdeleteriousefects when such fractions'arefurther treated by r-hydrogenolysis.

i In accordance-Withmy'inventionicharge stocks, usually aresiduum'with an' 'initial boiling-@point of 700 F. such as; foriexample;topped'crudesreduced crude, vacuum reduced'crudei'bottoms from propane deasphalting of reducedcrude, 'topped crude cracking residuum, naphtha cracking tar, and like materials containing parafIins-andaromatics, `are solvent extracted utilizing as-'extra-ctive solvents materials such as `sulfur dioxide, furfuralymethyl Cellosolve, and nitrobenzene; `It is preferable that the feed stocks are of such character that the aromatic' extract obtained therefrom comprises f20to 80 volum'eper centof the total. i For'example, in processing a stock such as an850" F. plus vacuum' reduced topped crude cracking "residuum containingfat leastf20 volume vper cent aromatics, thearomatic extract is 4desirablyof a gravity of 'not liorethan'abcut `10'API1and` preferablyl not `morelthan about 5 API. This feedstock may be'-extrac'ted either with only onesolvent orby a'dual solventprocess. The former processwill be discussed rst.

Y A charge of .the aboveA described Acharacter is liquid-liquid extracted at` knownizconditionyto provide a iparafnic fraction recoverediias'over- -head and an f aromatic` fraction recoveredJ fasi'ra. bottoms"l product. The paraflinic" fraction' :which contains 4only 4a .minor 4portion ofli-solv'ent'l'is stripped -of solventand thenA preferably `passed-to a hydrogenolysis zonewhereitis contacted with a* Ysulf -active catalyst" of the type- 'such-ias `riolybdenum` oxide on alu'mina or `on silicaialunri'ia -madeeither by impregnation or coprecipitaton.

Other catalysts may be used besidesthosev listed above. such as the sulfides ofmolybdenum-l-'and related materials, i preferably.' supportedu ini some manner. For the treatment'of .the'parainicffraction `preferable conditionsv are: ltemp'eratureil) to 900 F., pressure-*2000 toi5000 p; s; i.-(pr'e'fe'r ablyabove 3500 p; s. i); feed rate-0.5I to`4lliquid volumes per volume ofcatalyst per hour "(p'referably 1.5 to 3` liquid `volumes per '.volumelper hour) a hydrogen'circulation `rate `"of T5000 to 20,000 cubic feet per barrelof feed tothe'reactbr, and a per pass conversionof 40 to 60perfcentof ythe total feed. `Eluent Vis withdrawnfromfthe hydrogenolysis Azone and is separated a' manner such that thefhydrogen may be"recycled1to=the hydrogenolysis zone. The remaining eiiiuent is fractionated to obtain C4 and lighter hydrocarbons, gasoline, gas oil which may be used as diesel fuel or for a cracking stock, and residuum. The cuts -obtained by fractionation may be varied considerably depending on the materials desired and the feed and reaction conditions and are not to be limited by the above recitation. The residuum from the fractionation may be used as fuel oil or preferably may be recycled to the hydrogenolysis zone for further treating. This latter step is usually desirable because such residuum generally contains at least a portion of unreacted feed, and because it enhances the economy of the process.

rlihe aromatic fraction containing the extracting solvent is passed to a suitable solvent removal zone such as may comprise pressure reduction and/or heating, wherein the solvent is stripped from the aromatic material and from which the solvent is recycled to the extraction zone. The thus obtained aromatic fraction is then passed to a hydrogenolysis Zone for treatment under conditions different from those used in treating the parafnic material, Suitable operating conditions for the treatment of this material are: temperature, 900 to 950 F.; pressure, 200 to 5000 p. S. i. (preferably 2000 to 4000 p. s. i.); feed rate 0.5 to 4 liquid volumes per volume of catalyst per hour (preferably 1 to 2 liquid volumes per volume per hour) and a hydrogen circulation rate of 5000 to 10,000 cubic feet per barrel of feed. It is preferable that the particular operating conditions be chosen within the above ranges to produce conversion of the fresh charge from 60 to 90 per cent. The effluent from the hydrogenolysis zone is passed to a suitable high pressure separation zone wherein the hydrogen is recovered for recycle. The remaining products are then passed to fractionation wherein fractions of C4 and lighter, gasoline, gas oil, and residuum are obtained. Here again, applicant does not wish to be limited by the particular fractions recovered, the above being given merely to exemplify his invention. The residual fraction and the gas oil if desired, may be recycled to the hydrogenolysis step for further treatment inasmuch as it will contain at least some untreated material, or it may be recycled directly to .the extraction zone where it is introduced along with fresh feed.

As a second and preferred embodiment of my invention I practice the above discussed process utilizing two solvents, one for the aromatic hydrocarbons already discussed and one for the parainic hydrocarbons. Suitable solvents for the parafnic fraction are propane, butane, hexane, and gasoline or gas oil-boiling range materials. When such solvents are used, suitable recovery means must be employed to separate them from the fraction they extract for recycle. A still more preferred method of operation is to use as the second solvent, i. e. the solvent for the paraffns, the gasoline and/or gas oil obtained from fractionating the paraffin hydrogenolysis products. Inasmuch as the hydrogenolysis of the parans is operated under conditions to produce only a minimum of gasoline and inasmuch as such gasoline is not of a premium quality, this is a desirable use for such gasoline. Obviously, the quantity of gasoline or gas oil product will build up in such a process and in view of this it may either be used as a one-pass solvent without separation before fractionation or may be separated by suitable means and recycled. When the solvent is recycled, only a sufficient quantity may be recovered from the rainate in the stripping zone to take care of the extraction. The remaining portion may be allowed to pass on through to fractionation. In any event a certain quantity of the material will be withdrawn from the fractionation zone over and above that necessary for the extractive solvent. Such gasoline range materials may be advantageously treated by means not shown in the attached drawing such as reforming and the like.

A more complete understanding of my process may be obtained by referring to the attached schematic ow diagram of the preferred modification of my invention. The valves, pumps, and other similar equipment have not been included in the drawing to keep it as simple and easy to follow as possible, however, one skilled in the art may readily supply such equipment after reading the following discussion.

Refer now to the drawing. A feed material containing both aromatics and parafns is passed via line I0 to extraction Zone ll where it is contacted with a solventV for aromatics introduced Via line l2 and a solvent for paraflinsintroduced Via line I3. It is apparent from the drawing that contacting is by countercurrent flow, each of the solvents being introduced at the opposite end from which the fraction they selectively7 dissolve is removed. Extracted paraffin and solvent are removed from extraction zone Il via line I4 and are passed to stripping Zone l 6 where, by suitable means previously discussed and well within the skill of the art, the solvent is separated from the parafflns and is recycled to the extraction Zone via lines ll, 34, and I 3. The separated parailins are then passed from stripping zone |76 via lines I8, I9 and 20 to hydrogenolysis zone 2l. In this zone they are contacted with a suitable catalyst at the desired operating conditions selected from the ranges previously discussed, and are upgraded as desired. The treated materials are withdrawn from the catalyst zone by means of line 22 and are passed therethrough to high pressure separation zoneY 23 for the removal of hydrogen. Separated hydrogen is passed overhead and recycled to the hydrogenolysis zone via lines 24', 26, and 20. Fresh hydrogen may also be introduced via lines 25 and 20. The treated hydrocarbons are then recovered through line 2l and pass therefrom through line 28 to fractionation'zone 2Q. In this zone these materials are separated, generally into a C4 and lighter fraction recovered overhead through line 30, a gasoline fraction recovered through line 3 l, a cracking stock or diesel oil fraction recovered through line 32 and a residual fraction recovered through line I9.- This latter residual fraction is preferably recycled through line 20 back to the hydrogenolysis zone. Part of the gasoline fraction recovered fromzone 29 through line 3l is recycled to extraction zone I l through lines 34 and l3as one of the extractive solvents, Alternatively or in addition, part of the cracking stock recovered through line 32 may also be recycled for use as one of the solvents through lines 36, 34 and I3.

VThe aromatic fraction recovered from the bottom of extraction Zone ll via line 3l is passed to stripping zone 38 for removal of the solvent. This solvent is then recycled to zone Il Via lines 39 and l2. The separated aromatic fraction is then passed by means of lines 40, 4I, and 42 to hydrogenolysis Zone G3 where it is contacted in a hydrogen atmosphere with a suitable hydrogenolysis catalyst of the type described above.

stag-ait The treated materialis recoveredfrom this zone by means of line 44 and ispassed therethrough to high pressure separation zone"46 Where the hydrogen is separated andrecycled through lines 41 and 42 to hydrogenolysis zone 43. Fresh hydrogen is introduced to zone 43 by means of line 42. The product from separation zone 46 is passed by' means' of line48to fractionation v'zone 40 Where it is'separated into" suitable fractions. A Grand lighter "fractionis recovered through line 50,' a gasoline 'fraction is recovered via/ line 5|, a gas oil fractionis recovered'via line 52, and a residual fractionis recovered through line 53. Thisresidual fraction may be recycled either to hydrogenolysis zone 43 through lines 4| `and 42 or to extraction zoneV I I" along vvith the fresh feed through line I0. Part of the gas oil in line 52 may be similarly recycled, although some is usually Withdrawn and utilized, e. g. as feed to a carbon black process.

The following example illustrates some of the advantages of this invention. The reactants and their proportions and other specific ingredients are presented as being typical and should not be construed to limit this invention unduly.

Example An 11 API gravity vacuum reduced topped crude cracking residuum is solvent extracted utilizing furfural and subsequently produced paraiinic gasoline as solvents to produce a 17 API gravity parafnic fraction and a -3 API aromatic fraction. The 17 API gravity fraction is subjected to hydrogenolysis over a molybdena-alumina catalyst at a temperature of 875 F. and a pressure of 400 p. s. i. The feed rate is 2 volumes of liquid per volume of catalyst per hour. These conditions are chosen to provide a 50 per cent conversion per pass. The ultimate yields of products based on the charge are:

Gasoline-15 volume percent, clear octane number 38 400 to 600 F. gas oil-35 volume percent, cetane number 60 600 to 850 F. cracking stock- 46 volume percent,

API gravity 32, aniline point 207 F.

The -3 API gravity fraction is also subjected to hydrogenolysis over a molybdena-alumina catalyst but at 925 F. and a pressure of 4000 p. s. i. The space velocity utilized is 1.5 liquid volumes of charge per volume of catalyst per hour. The above conditions are selected to provide 80 per cent conversion of fresh feed per'pass. The ultimate yields of products are:

Gasoline-31 volume percent, octane number 71 400 Frigas oil, 20 vol. percent, cetane number 0, aniline point 8 F.

Hydrogenolysis of the charge without separation is carried out over a molybdena on alumina catalyst at 900 F. and at a 67 per cent conversion. Ultimate yields of products are:

Gasoline-23 volume percent, octane number 41 400 to 600 F. gas oil 24 volume percent, cetane number 45 600 to 880 F'. cracking stock 65 volume percent,

API gravity 24, aniline point 160 F.

A comparison of the above data shovvs that by operating in accordance With the teachings of my invention higher quality gasoline and gas oil or diesel fuel are obtained than those obtained When the total feed is treated together.

Although this process has been described and 6 exemplified j in terms of its preferred infifci'iffa-l tions, it is understood that'various minor changs maybe made Without departing from the spirit and scope of the disclosure and of the claims.

l. claim: l

1. A process for the'hydrogenolysis of a heavy residuum hydrocarbon oil containing both paraffins and aromatics, which 'compriseslextracting a heavy hydrocarbon oil'vvith a solventwhich selectively dissolves aromatics, passing the paraffin raffinate to a hydrogenolysis process "Where it is treated at a temperature in the range'of 850 to 900 F., a pressure in the range of 3500 `to 5000 p. s. i., a feed rate of 0.5 to 4 liquid volumes of charge per volume of catalyst per hour, and with a hydrogen circulation of 5000 to 20,000 cubic feet per barrel of feed, separating the Vproducts of this hydrogenolysis andrecovering `gasoline having an end boiling point'of 400 F. and" a good quality gas oil; separating the solvent from said aromatics, passing the aromatic extract to a hydrogenolysis process Where it is treated at different conditions at a temperature in the range of 900 to 950 F., a pressure on the range of 2000 to 4000 p. s. i., a feed rate of 0.5 to 4 liquid volumes of charge per volume of catalyst per hour, and with a hydrogen circulation rate in the range of 5,000 to 10,000 cubic feet per barrel of feed, separating the products of this second hydrogenolysis and recovering a good quality gasoline, and recycling the gasoline boiling range materials from the paraffin hydrogenolysis product to said extraction as a solvent for parains.

2. A process according to claim 1 wherein the reaction conditions in the hydrogenolysis steps are so selected that in the treatment of the parafns a per pass conversion of 40 to 60 per cent based on the total feed is maintained and in the treatment of the aromatics a per pass conversion of 60 to 90 per cent is maintained.

3. A process according to claim 1 wherein at least part of said gas oil from said parafn hydrogenolysis is recycled to the extraction zone as additional solvent for the parafns.

4. A hydrogenolysis process for treating heavy hydrocarbon oils containing parafiins and aromatics, which comprises passing an oil containing 20 to 80 per cent aromatics to an extraction zone, contacting said oil with a solvent for said aromatics and a solvent for the paraffins, recovering said paraffins and the solvent therefor and separating same, recycling separated solvent back to said extraction zone, passing the paraflins to a hydrogenolysis zone where they are treated in the presence of a molybdenum oxide-alumina hydrogenolysis catalyst at a temperature of 875 F., a pressure of 3500 to 5000 p. s. i., a feed rate of 1.5 to 3 liquid volumes per volume of catalyst, and with a hydrogen circulation rate of 5000 to 20,000 cubic feet per barrel of feed, passing efuent from said hydrogenolysis zone to a separation zone where unreacted hydrogen is flashed off for recycle, passing the eiiluent from said separation zone to a fractionation zone where it is divided into a C4 and lighter fraction, a gasoline fraction having an end boiling point of 400 F., a gas oil fraction of good quality, and a residue fraction, passing said residue back to said hydrogenolysis zone for further treatment, passing said gasoline back to said extraction zone as said solvent for parafnns; recovering the aromatics and the solvent therefor from said extraction zone and passing same to a separation zone Where the solvent is removed and recycled to said extraction zone, passing the aromatics from said separation zone to a second hydrogenolysis zone Where it is reacted at a temperature of 925 F., a pressure of 2000 to 4000 p. s. i., a feed rate of 1 to 2 liquid volumes per volume of catalyst per hour and a hydrogen circulation rate of 5000 to 10,000 cubic feet per barrel over a molybdenum oxide-alumina catalyst, passing the effluent from said second hydrogenolysis zone to a separation zone Where unreacted hydrogen is ashed oi for recycle, passing the eiiiuent from said separation zone to a fractionation zone where it is divided into a C4 and lighter fraction, a good quality gasoline fraction, a gas oil fraction, and a residue fraction, and recycling said residue fraction to said extraction zone for reprocessing.

5. A process according to claim 4 wherein the hydrogenolysis processes are carried out over molybdenum oxide-containing catalysts.

y WILLIAM C. LANNING.

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS Number Name Date 2,123,642 Gaylor July 12. 1938 2,149,900 Pier et al Mar. 7, 1939 2,335,684 Mayer Nov. 30, 1943 2,366,490 Cloud Jan. 2, 1945 2,374,102 Jahn et al Apr. 17, 1945 2,415,700 Meier Feb. 11, 1947 FOREIGN PATENTS Number Country Date 333,550 Great Britain Aug. 11, 1930 443,339

Great Britain Feb. 26, 1936 

1. A PROCESS FOR THE HYDROGENOLYSIS OF A HEAVY RESIDUUM HYDROCARBON OIL CONTAINING BOTH PARAFFINS AND AROMATICS, WHICH COMPRISES EXTRACTING A HEAVY HYDROCARBON OIL WITH A SOLVENT WHICH SELECTIVELY DISSOLVES AROMATICS, PASSING THE PARAFFIN RAFFINATE TO A HYDROGENOLYSIS PROCESS WHERE IT IS TREATED AT A TEMPERATURE IN THE RANGE OF 850 TO 900* F., A PRESSURE IN THE RANGE OF 3500 TO 5000 P.S.I., A FEED RATE OF 0.5 TO 4 LIQUID VOLUMES OF CHARGE PER VOLUME OF CATALYST PER HOUR, AND WITH A HYDROGEN CIRCULATION OF 5000 TO 20,000 CUBIC FEET PER BARREL OF FEED, SEPARATING THE PRODUCTS OF THIS HYDROGENOLYSIS AND RECOVERING GASOLINE HAVING AN END BOILING POINT OF 400* F. AND A GOOD QUALITY GAS OIL; SEPARATING THE SOLVENT FROM SAID AROMATICS, PASSING THE AROMATIC EXTRACT TO A HYDROGENOLYSIS PROCESS WHERE IT IS TREATED AT DIFFERENT CONDITIONS AT A TEMPERATURE IN THE RANGE OF 900* F., A PRESSURE ON THE RANGE OF 2000 TO 4000 P.S.I., A FEED RATE OF 0.5 TO 4 LIQUID VOLUMES OF CHARGE PER VOLUME OF CATALYST PER HOUR, AND WITH A HYDROGEN CIRCULATION RATE IN THE RANGE OF 5,000 TO 10,000 CUBIC FEET PER BARREL OF FEED, SEPARATING THE PRODUCTS OF THIS SECOND HYDROGENOLYSIS AND RECOVERING A GOOD QUALITY GASOLINE, AND RECYCLING THE GASOLINE BOILING RANGE MATERIALS FROM THE PARAFFIN HYDROGENOLYSIS PRODUCT TO SAID EXTRACTION AS A SOLVENT FOR PARAFFINS. 